U.S. patent application number 16/045712 was filed with the patent office on 2018-11-15 for resin composition containing surface-modified inorganic substance, thermally conductive material, and device.
This patent application is currently assigned to FUJIFILM Corporation. The applicant listed for this patent is FUJIFILM Corporation. Invention is credited to Keita TAKAHASHI.
Application Number | 20180327602 16/045712 |
Document ID | / |
Family ID | 59398238 |
Filed Date | 2018-11-15 |
United States Patent
Application |
20180327602 |
Kind Code |
A1 |
TAKAHASHI; Keita |
November 15, 2018 |
RESIN COMPOSITION CONTAINING SURFACE-MODIFIED INORGANIC SUBSTANCE,
THERMALLY CONDUCTIVE MATERIAL, AND DEVICE
Abstract
According to the present invention, there are provided a resin
composition containing a surface-modified inorganic substance,
which is obtained by performing surface modification on an
inorganic nitride or an inorganic oxide by using a boronic acid
compound, and an epoxy compound, a thermally conductive material
including a cured substance of the resin composition, and a device
including the thermally conductive material. The boronic acid
compound has, for example, an amino group, a thiol group, a
hydroxyl group, an isocyanate group, a carboxyl group, or a
carboxylic acid anhydride group. By using the resin composition of
the present invention, it is possible to provide a thermally
conductive material having excellent thermal conductivity and a
device having high durability.
Inventors: |
TAKAHASHI; Keita; (Kanagawa,
JP) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
FUJIFILM Corporation |
Tokyo |
|
JP |
|
|
Assignee: |
FUJIFILM Corporation
Tokyo
JP
|
Family ID: |
59398238 |
Appl. No.: |
16/045712 |
Filed: |
July 25, 2018 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
PCT/JP2017/002468 |
Jan 25, 2017 |
|
|
|
16045712 |
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C08K 9/04 20130101; C08K
2003/2227 20130101; C09K 5/14 20130101; C08G 65/22 20130101; C08K
2003/2296 20130101; C01B 21/068 20130101; C08K 5/14 20130101; C08K
2003/2241 20130101; C08L 101/00 20130101; C01B 21/064 20130101;
C08K 2003/282 20130101; C08K 2003/2237 20130101; C08K 2201/001
20130101; C01B 21/072 20130101; C08G 65/18 20130101; C08K 5/55
20130101; C08L 63/00 20130101; C08J 5/18 20130101; C08K 3/38
20130101; C08K 3/28 20130101; C08K 3/22 20130101; C08K 5/1515
20130101; C08L 63/00 20130101; C08K 9/04 20130101; C08K 9/04
20130101; C08L 63/00 20130101; C08K 5/14 20130101; C08L 63/00
20130101 |
International
Class: |
C08L 101/00 20060101
C08L101/00; C08K 5/1515 20060101 C08K005/1515; C08K 5/55 20060101
C08K005/55; C08K 9/04 20060101 C08K009/04 |
Foreign Application Data
Date |
Code |
Application Number |
Jan 26, 2016 |
JP |
2016-012617 |
Claims
1. A resin composition comprising; a surface-modified inorganic
substance which is obtained by performing surface modification on
one or more inorganic substances selected from the group consisting
of an inorganic nitride and an inorganic oxide by using a boronic
acid compound; and an epoxy compound.
2. The resin composition according to claim 1, wherein the surface
modification is modification based on the formation of a covalent
bond that the boronic acid compound forms with a surface of the
inorganic substance.
3. A resin composition comprising: one or more inorganic substances
selected from the group consisting of an inorganic nitride and an
inorganic oxide; a boronic acid compound; and an epoxy compound,
wherein the inorganic oxide is titanium oxide, aluminum oxide, or
zinc oxide, and the boronic acid compound is represented by General
Formula I or General Formula II, ##STR00037## in the formula, Z
represents an amino group, a thiol group, a hydroxyl group, an
isocyanate group, a carboxyl group, a carboxylic acid anhydride
group, a polymerizable group, a hydrogen atom, a halogen atom, a
quaternary ammonium group or a salt thereof, or a quaternary
pyridinium group, which may have a substituent, or a salt thereof,
X represents a linking group A, a linking group constituted with a
combination of two or more linking groups A, or a linking group
constituted with a combination of one or more linking groups A and
one or more linking groups B, linking group A is selected from the
group consisting of a divalent aliphatic hydrocarbon group which
may have a substituent, an arylene group which may have a
substituent, and a heteroarylene group which may have a
substituent, linking groups B is selected from the group consisting
of --O--, --CO--, --NH--, --CO--NH--, --COO--, and --O--COO--,
R.sup.1 and R.sup.2 each independently represent a hydrogen atom,
an aliphatic hydrocarbon group which may have a substituent, an
aryl group which may have a substituent, or a heteroaryl group
which may have a substituent, and R.sup.1 and R.sup.2 may be linked
to each other through an alkylene linking group, an arylene linking
group, or a linking group formed of a combination of these;
##STR00038## in the formula, Z represents an amino group, a thiol
group, a hydroxyl group, an isocyanate group, a carboxyl group, a
carboxylic acid anhydride group, a polymerizable group, a hydrogen
atom, a halogen atom, a quaternary ammonium group or a salt
thereof, or a quaternary pyridinium group which may have a
substituent or a salt thereof, X.sup.2 represents an (n+1)-valent
linking group obtained by further removing certain (n-1) hydrogen
atoms from the divalent linking group represented by X, R.sup.1 and
R.sup.2 each independently represent a hydrogen atom, an aliphatic
hydrocarbon group which may have a substituent, an aryl group which
may have a substituent, or a heteroaryl group which may have a
substituent, R.sup.1 and R.sup.2 may be linked to each other
through an alkylene linking group, an arylene linking group, or a
linking group formed of a combination of these, and n represents an
integer of equal to or greater than 2.
4. The resin composition according to claim 1, wherein the
inorganic substance is an inorganic nitride.
5. The resin composition according to claim 4, wherein the
inorganic nitride includes boron, aluminum, or silicon.
6. The resin composition according to claim 4, wherein the
inorganic nitride is boron nitride.
7. The resin composition according to claim 4, wherein the
inorganic nitride is aluminum nitride.
8. The resin composition according to claim 1, wherein the
inorganic substance is an inorganic oxide.
9. The resin composition according to claim 8, wherein the
inorganic oxide is titanium oxide, aluminum oxide, or zinc
oxide.
10. The resin composition according to claim 1, wherein the boronic
acid compound is represented by General Formula I, ##STR00039## in
the formula, Z represents an amino group, a thiol group, a hydroxyl
group, an isocyanate group, a carboxyl group, a carboxylic acid
anhydride group, a polymerizable group, a hydrogen atom, a halogen
atom, a quaternary ammonium group or a salt thereof, or a
quaternary pyridinium group, which may have a substituent, or a
salt thereof, X represents a divalent linking group including at
least one linking group A selected from the group consisting of a
divalent aliphatic hydrocarbon group which may have a substituent,
an arylene group which may have a substituent, and a heteroarylene
group which may have a substituent, R.sup.1 and R.sup.2 each
independently represent a hydrogen atom, an aliphatic hydrocarbon
group which may have a substituent, an aryl group which may have a
substituent, or a heteroaryl group which may have a substituent,
and R.sup.1 and R.sup.2 may be linked to each other through an
alkylene linking group, an arylene linking group, or a linking
group forming of a combination of these.
11. The resin composition according to claim 1, wherein the boronic
acid compound is represented by General Formula II; ##STR00040## in
the formula, Z represents an amino group, a thiol group, a hydroxyl
group, an isocyanate group, a carboxyl group, a carboxylic acid
anhydride group, a polymerizable group, a hydrogen atom, a halogen
atom, a quaternary ammonium group or a salt thereof, or a
quaternary pyridinium group which may have a substituent or a salt
thereof, X.sup.2 represents an (n+1)-valent linking group including
at least one linking group A selected from the group consisting of
a divalent aliphatic hydrocarbon group which may have a
substituent, an arylene group which may have a substituent, and a
heteroarylene group which may have a substituent, R.sup.1 and
R.sup.2 each independently represent a hydrogen atom, an aliphatic
hydrocarbon group which may have a substituent, an aryl group which
may have a substituent, or a heteroaryl group which may have a
substituent, R.sup.1 and R.sup.2 may be linked to each other
through an alkylene linking group, an arylene linking group, or a
linking group formed of a combination of these, and n represents an
integer of equal to or greater than 2.
12. The resin composition according to claim 1, wherein the boronic
acid compound has an amino group, a thiol group, a hydroxyl group,
an isocyanate group, a carboxyl group, or a carboxylic acid
anhydride group.
13. The resin composition according to claim 1, further comprising:
a curing agent having a group selected from the group consisting of
an amino group, a thiol group, a hydroxyl group, an isocyanate
group, a carboxyl group, and a carboxylic acid anhydride group.
14. The resin composition according to claim 13, wherein the
boronic acid compound has an oxiranyl group.
15. A thermally conductive material comprising: a cured substance
of the resin composition according to claim 1.
16. The thermally conductive material according to claim 15 that is
in the form of a sheet.
17. The thermally conductive material according to claim 16 that is
a heat dissipation sheet.
18. A device comprising: the thermally conductive material
according to claim 15.
19. A thermally conductive material comprising: a cured substance
of the resin composition according to claim 3.
20. A device comprising: the thermally conductive material
according to claim 19.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application is a continuation of PCT International
Application No. PCT/JP2017/002468 filed on Jan. 25, 2017, which
claims priority under 35 U.S.C. .sctn. 119 (a) to Japanese Patent
Application No. 2016-012617 filed on Jan. 26, 2016, the entire
contents of which are incorporated herein by reference.
BACKGROUND OF THE INVENTION
1. Field of the Invention
[0002] The present invention relates to a resin composition
containing a surface-modified inorganic substance. Furthermore, the
present invention relates to a thermally conductive material
containing a cured substance of the resin composition and a device
including the thermally conductive material.
2. Description of the Related Art
[0003] A surface-modified inorganic substance obtained by modifying
the surface of an inorganic substance such as an inorganic oxide or
an inorganic nitride is used in various fields as a pigment, a
catalyst, an electrode material, a semiconductor material, a heat
dissipation material, a thermally conductive material, a lubricant,
and the like.
[0004] Regarding the compounds used for surface modification of an
inorganic oxide, the surface modification based on the formation of
a chemical bond by a carboxylic acid such as a long-chain alkyl
fatty acid and an acid such as organic phosphonic acid or an
organic phosphoric acid ester through an acid-base reaction or the
surface modification based on the formation of a chemical bond with
an organic silane molecule through a silane coupling reaction is
known.
[0005] As a method for modifying the surface of an inorganic
nitride, JP2006-257392A discloses a method in which silane,
aluminate, or a titanate coupling agent is caused to react with the
surface of an inorganic nitride particle such that the surface of
the inorganic nitride particle is modified. Furthermore,
JP2001-192500A reports a method of mixing boron nitride with
1,4-phenylene diisocyanate and heating the mixture in a solvent
under reflux. In addition, JP4858470B describes a method of using a
compound, which has two reaction points including an anhydride
portion and an acid chloride portion, and an aromatic diamino
compound.
[0006] In recent years, a number of thermally conductive materials
have been developed which are obtained by performing curing or the
like on a resin composition prepared by mixing a surface-modified
inorganic substance with a resin binder. According to recent
reports, as the resin binder, in addition to a general epoxy
compound which has been used in the related art, a liquid crystal
compound is used in some cases (JP1999-323162A (JP-H11-323162A and
JP4118691B).
SUMMARY OF THE INVENTION
[0007] By the surface modification, the affinity or reactivity
between an inorganic substance and a resin binder contained in the
aforementioned resin composition is also improved. In a case where
a compound, which has the characteristics for modifying the surface
of an inorganic substance and exhibits excellent reactivity with
respect to a resin binder, is selected as a compound for modifying
the surface of an inorganic substance, a resin composition is
likely to be obtained which makes it possible to obtain a thermally
conductive material having thermal conductivity higher than that of
the resin compositions known in the related art.
[0008] An object of the present invention is to provide a resin
composition which makes it possible to obtain a thermally
conductive material having excellent thermal conductivity. Another
object of the present invention is to provide a thermally
conductive material having excellent thermal conductivity and a
device having high durability.
[0009] In order to achieve the aforementioned objects, the inventor
of the present invention attempted to modify the surface of an
inorganic substance by using various compounds. As a result, the
inventor obtained knowledge that in a case where a boronic acid
compound is used, the surface of an inorganic substance can be much
more easily modified than in a case where the methods disclosed in
JP2006-257392A, JP2001-192500A, and JP4858470B are used.
Furthermore, the inventor obtained knowledge that a cured
substance, which is prepared by mixing a surface-modified inorganic
substance obtained as above with various highly versatile epoxy
compounds as a resin binder, has high thermal conductivity. Based
on the knowledge, the inventor of the present invention repeated
examinations and has accomplished the present invention.
[0010] That is, the present invention provides [1] to [18]
described below.
[0011] [1] A resin composition comprising a surface-modified
inorganic substance which is obtained by performing surface
modification on one or more inorganic substances selected from the
group consisting of an inorganic nitride and an inorganic oxide by
using a boronic acid compound, and an epoxy compound.
[0012] [2] The resin composition described in [1], in which the
surface modification is modification based on the formation of a
covalent bond that the boronic acid compound forms with a surface
of the inorganic substance.
[0013] [3] A resin composition comprising one or more inorganic
substances selected from the group consisting of an inorganic
nitride and an inorganic oxide, a boronic acid compound, and an
epoxy compound.
[0014] [4] The resin composition described in any one of [1] to
[3], in which the inorganic substance is an inorganic nitride.
[0015] [5] The resin composition described in [4], in which the
inorganic nitride includes boron, aluminum, or silicon.
[0016] [6] The resin composition described in [4], in which the
inorganic nitride is boron nitride.
[0017] [7] The resin composition described in [4], in which the
inorganic nitride is aluminum nitride.
[0018] [8] The resin composition described in any one of [1] to
[3], in which the inorganic substance is an inorganic oxide.
[0019] [9] The resin composition described in [8], in which the
inorganic oxide is titanium oxide, aluminum oxide, or zinc
oxide.
[0020] [10] The resin composition described in any one of [1] to
[9], in which the boronic acid compound is represented by General
Formula I.
##STR00001##
[0021] In the formula, Z represents an amino group, a thiol group,
a hydroxyl group, an isocyanate group, a carboxyl group, a
carboxylic acid anhydride group, a polymerizable group, a hydrogen
atom, a halogen atom, a quaternary ammonium group or a salt
thereof, or a quaternary pyridinium group, which may have a
substituent, or a salt thereof, X represents a divalent linking
group including at least one linking group A selected from the
group consisting of a divalent aliphatic hydrocarbon group which
may have a substituent, an arylene group which may have a
substituent, and a heteroarylene group which may have a
substituent, R.sup.1 and R.sup.2 each independently represent a
hydrogen atom, an aliphatic hydrocarbon group which may have a
substituent, an aryl group which may have a substituent, or a
heteroaryl group which may have a substituent, and R.sup.1 and
R.sup.2 may be linked to each other through an alkylene linking
group, an arylene linking group, or a linking group formed of a
combination of these.
[0022] [11] The resin composition described in any one of [1] to
[9], in which the boronic acid compound is represented by General
Formula II;
##STR00002##
[0023] In the formula, Z represents an amino group, a thiol group,
a hydroxyl group, an isocyanate group, a carboxyl group, a
carboxylic acid anhydride group, a polymerizable group, a hydrogen
atom, a halogen atom, a quaternary ammonium group or a salt
thereof, or a quaternary pyridinium group which may have a
substituent or a salt thereof, X.sup.2 represents an (n+1)-valent
linking group including at least one linking group A selected from
the group consisting of a divalent aliphatic hydrocarbon group
which may have a substituent, an arylene group which may have a
substituent, and a heteroarylene group which may have a
substituent, R.sup.1 and R.sup.2 each independently represent a
hydrogen atom, an aliphatic hydrocarbon group which may have a
substituent, an aryl group which may have a substituent, or a
heteroaryl group which may have a substituent, R.sup.1 and R.sup.2
may be linked to each other through an alkylene linking group, an
arylene linking group, or a linking group formed of a combination
of these, and n represents an integer of equal to or greater than
2.
[0024] [12] The resin composition described in any one of [1] to
[11], in which the boronic acid compound has an amino group, a
thiol group, a hydroxyl group, an isocyanate group, a carboxyl
group, or a carboxylic acid anhydride group.
[0025] [13] The resin composition described in any one of [1] to
[12], further comprising a curing agent having a group selected
from the group consisting of an amino group, a thiol group, a
hydroxyl group, an isocyanate group, a carboxyl group, and a
carboxylic acid anhydride group.
[0026] [14] The resin composition described in [13], in which the
boronic acid compound has an oxiranyl group.
[0027] [15] A thermally conductive material comprising a cured
substance of the resin composition described in any one of [1] to
[14].
[0028] [16] The thermally conductive material described in [15]
that is in the form of a sheet. [17] The thermally conductive
material described in [16] that is a heat dissipation sheet.
[0029] [18] A device comprising the thermally conductive material
described in any one of [15] to [17].
[0030] According to the present invention, there is provided a
resin composition which makes it possible to obtain a thermally
conductive material having excellent thermal conductivity. By using
the resin composition of the present invention, it is possible to
provide a thermally conductive material having excellent thermal
conductivity and a device having high durability.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0031] Hereinafter, the present invention will be specifically
described.
[0032] In the present specification, "to" means that the numerical
values listed before and after "to" are of a lower limit and an
upper limit, respectively. In the present specification, the
description of "(meth)acryl group" means "either or both of an
acryl group and a methacryl group". The same is true for the
description of "(meth)acrylate" or the like.
[0033] In the present specification, "surface-modified" means a
state where an organic substance is adsorbed onto at least a
portion of the surface of an inorganic substance. The way the
organic substance is adsorbed is not particularly limited, and the
organic substance may be in a bonded state. That is,
"surface-modified" includes a state where an organic group obtained
by the dissociation of a portion of an organic substance forms a
bond with the surface of an inorganic substance. The bond may be
any one of a covalent bond, a coordinate bond, an ionic bond, a
hydrogen bond, a van der Waals bond, and a metallic bond, but is
preferably a covalent bond. In the "surface-modified" state, a
monolayer may be formed on at least a portion of the surface. The
monolayer is a monolayer film formed by the chemical adsorption of
organic molecules, and is known as Self-Assembled Monolayer (SAM).
The organic substance is a so-called organic compound, and means a
carbon atom-containing compound excluding carbon monoxide, carbon
dioxide, carbonate, and the like that are customarily classified as
an inorganic compound. In the present specification, the
"surface-modified" state may be established on only a portion of
the surface of an inorganic substance or on the entirety of the
surface of an inorganic substance.
[0034] In the present specification, "surface-modified inorganic
substance" means an inorganic substance whose surface is modified,
that is, a substance in which an organic substance is adsorbed onto
the surface of an inorganic substance.
[0035] <Resin Composition>
[0036] The resin composition of the present invention contains a
surface-modified inorganic substance and an epoxy compound.
[0037] The resin composition may contain one kind of
surface-modified inorganic substance or two or more kinds of
surface-modified inorganic substances. Furthermore, the resin
composition may contain one kind of epoxy compound or two or more
kinds of epoxy compounds.
[0038] The resin composition may contain, in addition to the
surface-modified inorganic substance and the epoxy compound, a
curing agent, another main agent (an acryl resin monomer or the
like), a curing accelerator, and the like. In the present
specification, the curing agent means a compound having a
functional group selected from a hydroxyl group, an amino group, a
thiol group, an isocyanate group, a carboxyl group, and a
carboxylic acid anhydride group, and the main agent means a
compound having a functional group selected from the group
consisting of a (meth)acryl group, an oxiranyl group, and an
oxetanyl group.
[0039] The resin composition may contain only a main agent or
contain a main agent and a curing agent.
[0040] <Surface-Modified Inorganic Substance>
[0041] In the surface-modified inorganic substance contained in the
resin composition of the present invention, a boronic acid compound
modifies the surface of an inorganic substance which is an
inorganic nitride or an inorganic oxide. It is preferable that the
boronic acid compound performs surface modification by conducting a
chemical reaction with the inorganic substance. Typically, the
boronic acid compound may react with a --NH.sub.2 group or a --OH
group on the surface of an inorganic substance and form a bond
represented by --NH--B-- or a bond represented by --O--B--. For
example, in a case where the compound represented by General
Formula I which will be described later is used as the boronic acid
compound, organic chains represented by Z--X-- can exist on the
surface of the inorganic substance through the aforementioned bond.
The organic chains may then form a monolayer preferably in an
arrayed state.
[0042] The shape of the surface-modified inorganic substance is not
particularly limited, and may be granular, film-like, or
plate-like. The granular surface-modified inorganic substance may
be made into finer granules by using a treatment such as
dispersion. Furthermore, the surface-modified inorganic substance
may have the shape of a nanosheet, a nanotube, a nanorod, or the
like.
[0043] [Inorganic Substance]
[0044] As the inorganic substance in the surface-modified inorganic
substance of the present invention, an inorganic oxide or an
inorganic nitride is used. The inorganic substance may be an
inorganic oxynitride. It is preferable that the inorganic substance
in the surface-modified inorganic substance of the present
invention is an inorganic nitride. The shape of the inorganic
substance is not particularly limited, and may be granular,
film-like, or plate-like.
[0045] The granules may have a rice grain shape, a spherical shape,
a cubical shape, a spindle shape, a scale shape, an aggregated
shape, or an amorphous shape.
[0046] The inorganic oxide is not particularly limited, and
examples thereof include zirconium oxide (ZrO.sub.2), titanium
oxide (TiO.sub.2), silicon oxide (SiO.sub.2), aluminum oxide
(Al.sub.2O.sub.3), iron oxide (Fe.sub.2O.sub.3, FeO, or
Fe.sub.3O.sub.4), copper oxide (CuO or Cu.sub.2O), zinc oxide
(ZnO), yttrium oxide (Y.sub.2O.sub.3), niobium oxide
(Nb.sub.2O.sub.5), molybdenum oxide (MoO.sub.3), indium oxide
(In.sub.2O.sub.3 or In.sub.2O), tin oxide (SnO.sub.2), tantalum
oxide (Ta.sub.2O.sub.5), tungsten oxide (WO.sub.3 or
W.sub.2O.sub.5), lead oxide (PbO or PbO.sub.2), bismuth oxide
(Bi.sub.2O.sub.3), cerium oxide (CeO.sub.2 or Ce.sub.2O.sub.3),
antimony oxide (Sb.sub.2O.sub.3 or Sb.sub.2O.sub.5), germanium
oxide (GeO.sub.2 or GeO), lanthanum oxide (La.sub.2O.sub.3),
ruthenium oxide (RuO.sub.2), and the like.
[0047] The above inorganic oxides may be used singly, or plural
kinds thereof may be used in combination.
[0048] The inorganic oxide is preferably titanium oxide, aluminum
oxide, or zinc oxide.
[0049] The inorganic oxide in the surface-modified inorganic
substance of the present invention may be an oxide generated in a
case where a metal prepared as a non-oxide is oxidized due to the
environment or the like.
[0050] The inorganic nitride is not particularly limited, and
examples thereof include boron nitride (BN), carbon nitride
(C.sub.3N.sub.4), silicon nitride (Si.sub.3N.sub.4), gallium
nitride (GaN), indium nitride (InN), aluminum nitride (AlN),
chromium nitride (Cr.sub.2N), copper nitride (Cu.sub.3N), iron
nitride (Fe.sub.4N), iron nitride (Fe.sub.3N), lanthanum nitride
(LaN), lithium nitride (Li.sub.3N), magnesium nitride
(Mg.sub.3N.sub.2), molybdenum nitride (Mo.sub.2N), niobium nitride
(NbN), tantalum nitride (TaN), titanium nitride (TiN), tungsten
nitride (W.sub.2N), tungsten nitride (WN.sub.2), yttrium nitride
(YN), zirconium nitride (ZrN), and the like.
[0051] The above inorganic nitrides may be used singly, or plural
kinds thereof may be used in combination.
[0052] The inorganic nitride in the surface-modified inorganic
substance of the present invention preferably includes aluminum,
boron, or silicon, and is preferably aluminum nitride, boron
nitride, or silicon nitride.
[0053] [Boronic Acid Compound]
[0054] The surface modification of the surface-modified inorganic
substance is performed using a boronic acid compound. The boronic
acid compound has a structure in which one or more hydroxyl groups
of boric acid are substituted with an organic group such as a
hydrocarbon group. By being adsorbed onto an inorganic substance
generally through the boron portion, the boronic acid compound
modifies the surface of an inorganic substance. The boronic acid
compound may be a compound represented by General Formula I, for
example.
##STR00003##
[0055] In General Formula I, Z represents an amino group, a thiol
group, a hydroxyl group, an isocyanate group, a carboxyl group, a
carboxylic acid anhydride group, a polymerizable group, a hydrogen
atom, a halogen atom, a quaternary ammonium group or a salt
thereof, or a quaternary pyridinium group or a salt thereof. The
quaternary pyridinium group may have a substituent.
[0056] In the present specification, an oxiranyl group is a
functional group referred to as an epoxy group as well. The
oxiranyl group may be a group including oxacyclopropane (oxirane),
and also includes a group, in which two adjacent carbon atoms in a
saturated hydrocarbon ring group form an oxirane ring by being
bonded to each other through an oxo group (--O--), and the like,
for example.
[0057] In the present specification, in a case where "hydroxyl
group" is exemplified as a functional group, the hydroxyl group is
preferably a hydroxyl group directly bonded to an aromatic ring
such as a phenyl group. Furthermore, the carboxylic acid anhydride
group may be a substituent obtained by removing any hydrogen atom
from an acid anhydride such as maleic acid anhydride, phthalic acid
anhydride, pyromellitic acid anhydride, or trimellitic acid
anhydride.
[0058] X represents a divalent linking group. X contains at least
one linking group A selected from the group consisting of a
divalent aliphatic hydrocarbon group which may have a substituent,
an arylene group which may have a substituent, and a heteroarylene
group which may have a substituent. X may contain one or more
linking groups B selected from the group consisting of --O--,
--CO--, --NH--, --CO--NH--, --COO--, and --O--COO--. That is, X is
the linking group A, a linking group constituted with a combination
of two or more linking groups A, or a linking group constituted
with a combination of one or more linking groups A and one or more
linking groups B.
[0059] R.sup.1 and R.sup.2 each independently represent a hydrogen
atom, an aliphatic hydrocarbon group which may have a substituent,
an aryl group which may have a substituent, or a heteroaryl group
which may have a substituent.
[0060] R.sup.1 and R.sup.2 may be linked through an alkylene
linking group, an arylene linking group, or a linking group as a
combination of an alkylene linking group and an arylene linking
group.
[0061] The divalent aliphatic hydrocarbon group which may have a
substituent includes an alkylene group which may have a substituent
and an alkenylene group which may have a substituent.
[0062] The aliphatic hydrocarbon group which may have a substituent
that is represented by each of R.sup.1 and R.sup.2 include an alkyl
group which may have a substituent, an alkenyl group which may have
a substituent, and an alkynyl group which may have a
substituent.
[0063] In the present specification, the alkyl group may be linear,
branched, or cyclic. The number of carbon atoms in the alkyl group
is preferably 1 to 30, and more preferably 2 to 10. Specific
examples of the alkyl group include a methyl group, an ethyl group,
a propyl group, a butyl group, a pentyl group, a hexyl group, a
heptyl group, an octyl group, a nonyl group, a decyl group, an
undecyl group, a dodecyl group, a tridecyl group, a hexadecyl
group, an octadecyl group, an eicosyl group, an isopropyl group, an
isobutyl group, a sec-butyl group, a tert-butyl group, an isopentyl
group, a neopentyl group, a 1-methylbutyl group, an isohexyl group,
a 2-methyhexyl group, a cyclopentyl group, a cyclohexyl group, a
1-adamantyl group, a 2-norbornyl group, and the like. The above
description relating to the alkyl group is also applied to other
groups such as an alkyl group-containing alkoxy group. The alkylene
group is a group obtained by removing a certain hydrogen atom from
the alkyl group, and examples of the alkylene group include the
groups obtained by removing a certain hydrogen atom from each of
the aforementioned examples of the alkyl group.
[0064] In the present specification, the alkenyl group may be
linear, branched, or cyclic. The number of carbon atoms in the
alkenyl group is preferably 2 to 30, and more preferably 2 to 10.
Specific examples of the alkenyl group include a vinyl group, a
1-propenyl group, a 1-butenyl group, a 1-methyl-1-propenyl group, a
1-cyclopentenyl group, a 1-cyclohexenyl group, and the like. The
above description relating to the alkenyl group is also applied to
other groups containing the alkenyl group. The alkenylene group is
a group obtained by removing a certain hydrogen atom from the
alkenyl group, and examples of the alkenylene group include the
groups obtained by removing a certain hydrogen atom from each of
the aforementioned examples of the alkenyl group.
[0065] The number of carbon atoms in the alkynyl group is
preferably 2 to 30, and more preferably 2 to 10. Specific examples
of the alkynyl group include an ethynyl group, a 1-propynyl group,
a 1-butynyl group, a 1-octynyl group, and the like.
[0066] The aryl group may be a monocyclic group or a ring-fused
group containing two or more rings. The number of carbon atoms in
the aryl group is preferably 5 to 18, and more preferably 5 to 10.
Specific examples of the aryl group include a phenyl group, a
naphthyl group, an anthryl group, a phenanthryl group, an indenyl
group, an acenaphthenyl group, a fluorenyl group, a pyrenyl group,
and the like. The arylene group is a group obtained by removing any
hydrogen atom from the aryl group, and examples of the arylene
group include the groups obtained by removing any hydrogen atom
from each of the aforementioned examples of the aryl group.
[0067] Examples of the heteroaryl group include heteroaryl groups
obtained by removing one hydrogen atom on a heterocyclic aromatic
ring containing one or more hetero atoms selected from the group
consisting of a nitrogen atom, an oxygen atom, and a sulfur atom.
Specific examples of the heterocyclic aromatic ring containing one
or more hetero atoms selected from the group consisting of a
nitrogen atom, an oxygen atom, and a sulfur atom include pyrrole,
furan, thiophene, pyrazole, imidazole, triazole, oxazole,
isoxazole, oxadiazole, thiazole, thiadiazole, indole, carbazole,
benzofuran, dibenzofuran, thianaphthene, dibenzothiophene, indazole
benzimidazole, anthranyl, benzisoxazole, benzoxazole,
benzothiazole, purine, pyridine, pyridazine, pyrimidine, pyrazine,
triazine, quinoline, acridine, isoquinoline, phthalazine,
quinazoline, quinoxaline, naphthyridine, phenanthroline, pteridine,
and the like. The heteroarylene group is a group obtained by
removing a certain hydrogen atom from the heteroaryl group, and
examples of the heteroarylene group include the groups obtained by
removing a certain hydrogen atom from each of the aforementioned
examples of the heteroaryl group.
[0068] In the present specification, in a case where the
description of "may have a substituent" appears, the type of a
substituent, the position of a substituent, and the number of
substituents are not particularly limited. The number of
substituents may, for example, be 1, 2, 3, or greater. Examples of
the substituent include a group of monovalent nonmetallic atoms
excluding hydrogen, and the substituent can be selected from the
following substituent group Y for example.
[0069] Substituent group Y: halogen atom (--F, --Br, --Cl, or --I),
a hydroxyl group, an alkoxy group, an aryloxy group, a mercapto
group, an alkylthio group, an arylthio group, an alkyldithio group,
an aryldithio group, an amino group, a N-alkylamino group, a
N,N-dialkylamino group, a N-arylamino group, a N,N-diarylamino
group, a N-alkyl-N-arylamino group, an acyloxy group, a
carbamoyloxy group, a N-alkylcarbamoyloxy group, a
N-arylcarbamoyloxy group, a N,N-dialkylcarbamoyloxy group, a
N,N-diarylcarbamoyloxy group, a N-alkyl-N-arylcarbamoyloxy group,
an alkylsulfoxy group, an arylsulfoxy group, an acylthio group, an
acylamino group, a N-alkylacylamino group, a N-arylacylamino group,
a ureide group, a N'-alkylarylureide group, a N',N'-dialkylureide
group, a N'-arylureide group, a N',N'-diarylureide group, a
N'-alkyl-N-arylureide group, a N-alkylureide group, a N-arylureide
group, a N'-alkyl-N-alkylureide group, a N'-alkyl-N-arylureide
group, a N',N'-dialkyl-N-alkylureide group, a
N',N'-dialkyl-N-arylureide group, a N'-aryl-N-alkylureide group, a
N'-aryl-N-arylureide group, a N',N'-diaryl-N-alkylureide group, a
N',N'-diaryl-N-arylureide group, a N'-alkyl-N'-aryl-N-alkylureide
group, a N'-alkyl-N'-aryl-N-arylureide group, an
alkoxycarbonylamino group, an aryloxycarbonylamino group, a
N-alkyl-N-alkoxycarbonylamino group, a
N-alkyl-N-aryloxycarbonylamino group, a
N-aryl-N-alkoxycarbonylamino group, a N-aryl-N-aryloxycarbonylamino
group, a formyl group, an acyl group, a carboxyl group and a
conjugated base group thereof, an alkoxycarbonyl group, an
aryloxycarbonyl group, a carbamoyl group, a N-alkylcarbamoyl group,
a N,N-dialkylcarbamoyl group, a N-arylcarbamoyl group, a
N,N-diarylcarbamoyl group, a N-alkyl-N-arylcarbamoyl group, an
alkylsufinyl group, an arylsulfinyl group, an alkylsulfonyl group,
an arylsulfonyl group, a sulfo group (--SO.sub.3H) and a conjugated
base group thereof, an alkoxysulfonyl group, an aryloxysulfonyl
group, a sulfinamoyl group, a N-alkylsulfinamoyl group, a
N,N-dialkylsulfinamoyl group, a N-arylsulfinamoyl group, a
N,N-diarylsulfinamoyl group, a N-alkyl-N-arylsulfinamoyl group, a
sulfamoyl group, a N-alkylsulfamoyl group, a N,N-dialkylsulfamoyl
group, a N-arylsulfamoyl group, a N,N-diarylsulfamoyl group, a
N-alkyl-N-arylsulfamoyl group, a N-acylsulfamoyl group and a
conjugated base group thereof, a N-alkylsulfonylsulfamoyl group
(--SO.sub.2NHSO.sub.2(alkyl)) and a conjugated base group thereof,
a N-arylsulfonylsulfamoyl group (--SO.sub.2NHSO.sub.2(aryl)) and a
conjugated base group thereof, a N-alkylsulfonylcarbamoyl group
(--CONHSO.sub.2(alkyl)) and a conjugated base group thereof, a
N-arylsulfonylcarbamoyl group (--CONHSO.sub.2(aryl)) and a
conjugated base group thereof, an alkoxysilyl group
(--Si(Oalkyl).sub.3), an aryloxysilyl group (--Si(Oaryl).sub.3), a
hydroxysilyl group (--Si(OH).sub.3) and a conjugated base group
thereof, a phosphono group (--PO.sub.3H.sub.2) and a conjugated
base group thereof, a dialkylphosphono group
(--PO.sub.3(alkyl).sub.2), a diarylphosphono group
(--PO.sub.3(aryl).sub.2), an alkylarylphosphono group
(--PO.sub.3(alkyl)(aryl)), a monoalkylphosphono group
(--PO.sub.3H(alkyl)) and a conjugated base group thereof, a
monoarylphosphono group (--PO.sub.3H(aryl)) and a conjugated base
group thereof, a phosphonooxy group (--OPO.sub.3H.sub.2) and a
conjugated base group thereof, a dialkylphosphonooxy group
(--OPO.sub.3(alkyl).sub.2), a diarylphosphonooxy group
(--OPO.sub.3(aryl).sub.2), an alkylarylphosphonooxy group
(--OPO.sub.3(alkyl)(aryl)), a monoalkylphosphonooxy group
(--OPO.sub.3H(alkyl)) and a conjugated base group thereof, a
monoarylphosphonooxy group (--OPO.sub.3H(aryl)) and a conjugated
base group thereof, a cyano group, a nitro group, an aryl group, an
alkenyl group, and an alkynyl group.
[0070] These substituents may form a ring with each other if
possible or may form a ring by being bonded to the group
substituted with the substituents.
[0071] Examples of the polymerizable group include a (meth)acrylate
group, a styryl group, a vinyl ketone group, a butadiene group, a
vinyl ether group, an oxiranyl group, an aziridinyl group, an
oxetane group, and the like. Among these, a (meth)acrylate group, a
styryl group, an oxiranyl group, or an oxetane group is more
preferable, and a (meth)acrylate group or an oxiranyl group is even
more preferable.
[0072] R.sup.1 and R.sup.2 in General Formula I are preferably a
hydrogen atom.
[0073] X in General Formula I is preferably a linking group
containing a phenylene group which may have at least one
substituent, and more preferably a linking group having a partial
structure to which a phenylene group which may have two
substituents is linked through --COO--. Furthermore, X is
preferably a linking group containing an unsubstituted phenylene
group. It is particularly preferable that the unsubstituted
phenylene group is directly bonded to a boron atom of the boronic
acid.
[0074] Z in General Formula I is preferably an amino group, a thiol
group, a hydroxyl group, an isocyanate group, a carboxyl group, a
carboxylic acid anhydride group, a (meth)acrylate group, an
oxiranyl group, or a hydrogen atom, more preferably an amino group,
a thiol group, a hydroxyl group, an isocyanate group, a carboxyl
group, or a carboxylic acid anhydride group, and even more
preferably an amino group, a thiol group, or a hydroxyl group.
Particularly, in a case where the resin composition contains a
curing agent having a group selected from the group consisting of
an amino group, a thiol group, a hydroxyl group, an isocyanate
group, a carboxyl group, or carboxylic acid anhydride group as a
curing agent, Z in General Formula I is also preferably an oxiranyl
group.
[0075] The boronic acid compound preferably has a chain-like
structure, because then a monolayer is easily formed.
[0076] Preferred examples of the boronic acid compound represented
by General Formula I will be shown below, but the present invention
is not limited thereto.
##STR00004## ##STR00005## ##STR00006## ##STR00007## ##STR00008##
##STR00009## ##STR00010## ##STR00011## ##STR00012##
[0077] Furthermore, a boronic acid compound represented by the
following General Formula II may be used.
##STR00013##
[0078] In General Formula II, Z, R.sup.1, and R.sup.2 each have the
same definition as in General Formula I, and the preferred range
thereof is also the same.
[0079] X.sup.2 is an (n+1)-valent linking group obtained by further
removing certain (n-1) hydrogen atoms from the divalent linking
group represented by X described above. At this time, the preferred
range of X is the same as that described above. X.sup.2 is
preferably an (n+1)-valent linking group obtained by further
removing hydrogen atoms from either the linking group A or a
divalent linking group constituted with a combination of two or
more linking groups A. At this time, the linking group A is
preferably an arylene group which may have a substituent or a
heteroarylene group which may have a substituent, and more
preferably a phenyl group or a divalent group formed by removing
hydrogen atoms from pyrrole, furan, or thiophene.
[0080] n is an integer equal to or greater than 2. n is preferably
2 to 10, and more preferably 3.
##STR00014##
[0081] In the present specification, a compound, which is easily
decomposed by being brought into contact with an inorganic
substance or easily decomposed in a solvent and generates the
aforementioned boronic acid compound, is also included in the
boronic acid compound.
[0082] Examples of such a compound include a compound in which the
hydrogen of one or two hydroxyl groups bonded to a boron in the
boronic acid compound is substituted with a substituent other than
a hydrogen atom, and a compound which has, instead of the boronic
acid (--B(OH).sub.2) moiety of the boronic acid compound, a moiety
having a structure that brings about the same effect as
(--B(OH).sub.2) through equilibrium or adsorption in a case of
contacting the inorganic substance. Specific examples of the
compound which is easily decomposed and generates the boronic acid
compound by being brought into contact with an inorganic substance
include compounds having a partial structure represented by any of
the following formulae. All of the partial structures represented
by the following formulae may have a substituent in a substitutable
moiety.
##STR00015##
[0083] As the boronic acid compound, a boronic acid compound is
also preferable which is easily decomposed by being brought into
contact with an inorganic substance or easily decomposed in a
solvent and generates the boronic acid compound represented by
General Formula I or General Formula II described above. Examples
of such a compound include the following ones.
##STR00016##
[0084] As the boronic acid compound, a commercial boronic acid
compound may be used as it is. Alternatively, the boronic acid
compound may be synthesized by using a boronic acid compound having
a substituent as a raw material through a general synthesis
reaction such as esterification, amidation, or alkylation. For
example, the boronic acid compound can be synthesized from a halide
(such as aryl bromide) by using n-butyl lithium and trialkoxyborane
(such as trimethoxyborane) or synthesized by performing a Wittig
reaction using metallic magnesium.
[0085] [Method for Manufacturing Surface-Modified Inorganic
Substance]
[0086] The surface-modified inorganic substance can be easily
manufactured by making a contact between an inorganic substance and
the boronic acid compound. The contact between the inorganic
substance and the boronic acid compound can be established by, for
example, stirring a solution containing an inorganic nitride or an
inorganic oxide and the boronic acid compound. Particularly, in a
case where the inorganic nitride or the inorganic oxide is
granular, it is preferable to make the contact by stirring.
[0087] A solvent of the aforementioned solution is not particularly
limited, but is preferably an organic solvent. Examples of the
organic solvent include ethyl acetate, methyl ethyl ketone,
dichloromethane, tetrahydrofuran (THF), and the like.
[0088] The aforementioned solution may contain other components,
such as an epoxy compound, in the resin composition of the present
invention. From a composition containing an inorganic substance, a
boronic acid compound, and an epoxy compound, it is possible to
easily manufacture a resin composition containing a
surface-modified inorganic substance and an epoxy compound.
[0089] A mixing ratio between the inorganic substance and the
boronic acid compound may be determined in consideration of the
structure such as the structure and the surface area of the
inorganic substance, the aspect ratio of the molecule of the
boronic acid compound, and the like.
[0090] The stirring conditions are not particularly limited. For
example, stirring may be performed at room temperature or may be
performed for about 1 to 10 seconds at a stirring rotation speed of
about 50 rpm.
[0091] <Epoxy Compound>
[0092] The epoxy compound used in the present invention may be a
monomer that can be polymerized by curing the resin composition.
The epoxy compound has at least one oxiranyl group.
[0093] The epoxy compound may have a polymerizable group other than
an oxiranyl group, but it is preferable that the epoxy compound
contains only an oxiranyl group as a polymerizable group.
Furthermore, the epoxy compound may have a functional group other
than a polymerizable group. It is preferable that the epoxy
compound contains only an oxiranyl group as a functional group.
[0094] As the epoxy compound, it is possible to use various epoxy
resin monomers known in the related art. For example, it is
possible to use the epoxy resin monomer described in "0028" in
JP4118691B, the epoxy compound described in "0006" to "0011" in
JP2008-13759A, the epoxy resin mixture described in "0032" to
"0100" in JP2013-227451A, the epoxy compound described in "0048" to
"0054" in JP2016-801A, and the like. Furthermore, as the epoxy
compound, a liquid crystal compound which will be described later
may be used.
[0095] The content of the epoxy compound in the resin composition
with respect to the mass of total solid contents of the resin
composition (mass of the solid contents except for a solvent) is
preferably 10% by mass to 90% by mass, more preferably 20% by mass
to 70% by mass, and even more preferably 30% by mass to 60% by
mass.
[0096] [Liquid Crystal Compound]
[0097] As the epoxy compound, a liquid crystal compound may also be
used. The liquid crystal compound may be a rod-like liquid crystal
compound or a disk-like liquid crystal compound.
[0098] The liquid crystal compound used as the epoxy compound is a
polymerizable liquid crystal compound having at least one oxiranyl
group. The liquid crystal compound may have a polymerizable group
other than an oxiranyl group, but it is preferable that the liquid
crystal compound contains only an oxiranyl group as a polymerizable
group. Furthermore, the liquid crystal compound may have a
functional group other than a polymerizable group. The liquid
crystal compound preferably has two or more polymerizable groups
and preferably has two or more oxiranyl groups.
[0099] The resin composition of the present invention may contain a
liquid crystal compound that does not correspond to the epoxy
compound, in addition to the epoxy compound.
[0100] (Rod-Like Liquid Crystal Compound)
[0101] As the rod-like liquid crystal compound, azomethines,
azoxies, cyanobiphenyls, cyanophenyl esters, benzoic acid esters,
cyclohexane carboxylic acid phenyl esters, cyanophenyl
cyclohexanes, cyano-substituted phenylpyrimidines,
alkoxy-substituted phenylpyrimidines, phenyldioxanes, tolans, and
alkenylcyclohexyl benzonitriles are preferably used. In addition to
these low-molecular weight liquid crystal compounds, high-molecular
weight liquid crystal compounds can also be used. The
aforementioned high-molecular weight liquid crystal compounds are
polymer compounds obtained by polymerizing rod-like liquid crystal
compounds having a low-molecular weight reactive group. As rod-like
liquid crystal compounds that are particularly preferably used, a
rod-like liquid crystal compound represented by General Formula
(XXI) can be exemplified.
Q.sup.1-L.sup.111-A.sup.111-L.sup.113-M-L.sup.114-A.sup.112-L.sup.112-Q.-
sup.2 General Formula (XXI):
[0102] In the formula, Q.sup.1 and Q.sup.2 each independently
represent a polymerizable group, and L.sup.111, L.sup.112,
L.sup.113, and L.sup.114 each independently represent a single bond
or a divalent linking group. A.sup.111 and A.sup.112 each
independently represent a spacer group having 2 to 20 carbon atoms.
M represents a mesogenic group.
[0103] At least one of Q.sup.1 and Q.sup.2 preferably represents an
oxiranyl group. It is more preferable that both of Q.sup.1 and
Q.sup.2 represent an oxiranyl group.
[0104] As the divalent linking group represented by L.sup.111,
L.sup.112, L.sup.113, and L.sup.114, a divalent linking group is
preferable which is selected from the group consisting of --O--,
--S--, --NR.sup.112--, --CO--O--, --O--CO--O--, --CO--NR.sup.112--,
--NR.sup.112--CO--, --O--CO--, --O--CO--NR.sup.112--,
--NR.sup.112--CO--O--, and NR.sup.112--CO--NR.sup.112--. R.sup.112
is an alkyl group having 1 to 7 carbon atoms or a hydrogen atom. In
Formula (I), Q.sup.1-L.sup.111 and Q.sup.2-L.sup.111- preferably
each represent CH.sub.2.dbd.CH--CO--O--,
CH.sub.2.dbd.C(CH.sub.3)--CO--O--, or
CH.sub.2.dbd.C(Cl)--CO--O--CO--O--, and most preferably each
represent CH.sub.2=CH--CO--O--.
[0105] A.sup.111 and A.sup.112 each represent a spacer group having
2 to 20 carbon atoms. A.sup.111 and A.sup.112 preferably each
represent an alkylene group having 2 to 12 carbon atoms, an
alkenylene group, or an alkynylene group, and particularly
preferably each represent an alkylene group. The spacer group is
preferably in the form of a chain, and may include oxygen atoms or
sulfur atoms that are not adjacent to each other. Furthermore, the
spacer group may have a substituent, and may be substituted with a
halogen atom (fluorine, chlorine, or bromine), a cyano group, a
methyl group, or an ethyl group.
[0106] Examples of the mesogenic group represented by M include all
the known mesogenic groups. Particularly, a group represented by
General Formula (XXII) is preferable.
--(-W.sup.1-L.sup.115).sub.n-W.sup.2-- General Formula (XXII):
[0107] In the formula, W.sup.1 and W.sup.2 each independently
represent a divalent cyclic alkylene or alkenylene group, a
divalent aryl group, or a divalent heterocyclic group, L.sup.115
represents a single bond or a linking group. Specific examples of
the linking group include the specific examples of the groups
represented by L.sup.111 to L.sup.114 in Formula (XXI),
--CH.sub.2--O--, and --O--CH.sub.2--. n represents 1, 2, or 3.
[0108] Examples of W.sup.1 and W.sup.2 include 1,4-cyclohexanediyl,
1,4-phenylene, pyrimidine-2,5-diyl, pyridine-2,5-diyl,
1,3,4-thiadiazole-2,5-diyl, 1,3,4-oxadiaole-2,5-diyl,
naphthalene-2,6-diyl, naphthalene-1,5-diyl, thiophene-2,5-diyl, and
pyridazine-3,6-diyl. In a case where W.sup.1 and W.sup.2 represent
1,4-cyclohexanediyl, there may be constitutional isomers of a
trans-isomer and a cis-isomer. Any of these isomers may be adopted,
or a mixture in which the isomers are mixed at any ratio may be
adopted. The isomer is more preferably a trans-isomer. Each of
W.sup.1 and W.sup.2 may have a substituent. Examples of the
substituent include a halogen atom (fluorine, chlorine, bromine, or
iodine), a cyano group, an alkyl group having 1 to 10 carbon atoms
(a methyl group, an ethyl group, a propyl group, or the like), an
alkoxy group having 1 to 10 carbon atoms (a methoxy group, an
ethoxy group, or the like), an acyl group having 1 to 10 carbon
atoms (a formyl group, an acetyl group, or the like), an
alkoxycarbonyl group having 1 to 10 carbon atoms (a methoxycarbonyl
group, an ethoxycarbonyl group, or the like), an acyloxy group
having 1 to 10 carbon atoms (an acetyloxy group, a propionyloxy
group, or the like), a nitro group, a trifluoromethyl group, a
difluoromethyl group, and the like.
[0109] Examples of those preferred as the basic skeleton of the
mesogenic group represented by General Formula (XXII) described
above will be shown below, and these may be substituted with the
aforementioned substituent.
##STR00017## ##STR00018##
[0110] The compound represented by General Formula (XXI) can be
synthesized with reference to the method described in
JP1999-513019A (JP-H11-513019A) (WO97/00600) and
JP2013-227451A.
[0111] The rod-like liquid crystal compound may be a monomer having
the mesogenic group described in JP1999-323162A (JP-H11-323162A)
and JP4118691B.
[0112] (Disk-Like Liquid Crystal Compound)
[0113] The disk-like liquid crystal compound has a disk-like
structure in at least a portion thereof. The disk-like structure
refers to a compound which has at least an aromatic ring and can
form a columnar structure by forming a stacking structure based on
the intermolecular .pi.-.pi. interaction. Specific examples of the
disk-like structure include the triphenylene structure described in
Angew. Chem. Int. Ed. 2012, 51, 7990-7993 or JP1995-306317A
(JP-H07-306317A), the trisubstituted benzene structure described in
JP2007-2220A or JP2010-244038A, and the like.
[0114] It is also preferable that the resin composition of the
present invention contains a compound which has the aforementioned
disk-like structure but does not exhibit liquid crystallinity.
[0115] The inventor of the present invention has found that the
compound having a disk-like structure brings about high thermal
conductivity. Regarding such high thermal conductivity, the
inventor does not stick to a specific theory but considers that
while the rod-like compound can only linearly (one-dimensionally)
conduct heat, the disk-like compound can flatwise
(two-dimensionally) conduct heat in a normal direction, and
accordingly, the number of heat conduction paths increase, and the
thermal conductivity is improved.
[0116] Furthermore, by the addition of the compound having a
disk-like structure, the heat resistance of a cured substance of
the resin composition can be improved. In order to improve the heat
resistance, it is more preferable that the compound having a
disk-like structure have three or more functional groups.
[0117] It is preferable that disk-like liquid crystal compound has
three or more functional groups. The cured substance of the resin
composition containing a monomer having three or more functional
groups tends to have a high glass transition temperature and high
heat resistance. Compared to a compound having a rod-like
structure, the disk-like compound more likely to have three or more
functional groups without affecting the characteristics of a
mesogenic portion. The number of functional groups in the disk-like
compound is preferably equal to or smaller than 8, and more
preferably equal to or smaller than 6. It is preferable that all
the functional groups are oxiranyl groups.
[0118] As the disk-like compound, it is preferable to use a
compound represented by General Formula (XI) or a compound
represented by General Formula (XII) shown below.
##STR00019##
[0119] In the formula, R.sup.12, R.sup.13, R.sup.14, R.sup.15, and
R.sup.16 each independently represent *--X.sup.11-L.sup.11-P.sup.11
or *--X.sup.12--Y.sup.12, * represents a position bonded to a
triphenylene ring, two or more among R.sup.11, R.sup.12, R.sup.13,
R.sup.14, R.sup.15 and R.sup.16 represent
*--X.sup.11-L.sup.11-P.sup.11, X.sup.11 and X.sup.12 each
independently represent a single bond, --O--, --C(.dbd.O)--,
--OC(.dbd.O)--, --OC(.dbd.O)O--, --OC(.dbd.O)NH--, --OC(.dbd.O)S--,
--C(.dbd.O)O--, --C(.dbd.O)NH--, --C(.dbd.O)S--, --NHC(.dbd.O)--,
--NHC(.dbd.O)O--, --NHC(.dbd.O)NH--, --NHC(.dbd.O)S--, --S--,
--SC(.dbd.O)--, --SC(.dbd.O)O--, --SC(.dbd.O)NH--, or
--SC(.dbd.O)S--, L.sup.11 represents a divalent linking group or a
single bond, P.sup.11 represents a substituent selected from the
group consisting of a (meth)acryl group, an oxiranyl group, an
oxetanyl group, a hydroxyl group, an amino group, a thiol group, an
isocyanate group, a carboxyl group, and a carboxylic acid anhydride
group, Y.sup.12 represents a hydrogen atom, a linear, branched, or
cyclic alkyl group having 1 to 20 carbon atoms, or a group obtained
in a case where one methylene group or two or more methylene groups
in a linear, branched, or cyclic alkyl group having 1 to 20 carbon
atoms are substituted with --O--, --S--, --NH--, --N(CH.sub.3)--,
--C(.dbd.O)--, --OC(.dbd.O)--, or --C(.dbd.O)O--.
[0120] It is preferable that three or more out of R.sup.11,
R.sup.12, R.sup.13, R.sup.14, R.sup.15, and R.sup.16 represent
*--X.sup.11-L.sup.11-P.sup.11. Particularly, it is preferable that
any one or more out of R.sup.11 and R.sup.12, any one or more out
of R.sup.13 and R.sup.14, and any one or more out of R.sup.15 and
R.sup.16 represent *--X.sup.11-L.sup.11-P.sup.11. It is more
preferable that all of R.sup.11, R.sup.12, R.sup.13, R.sup.14,
R.sup.15, and R.sup.16 represent *--X.sup.11-L.sup.11-P.sup.11. It
is particularly preferable that all of R.sup.11, R.sup.12,
R.sup.13, R.sup.14, R.sup.15, and R.sup.16 are the same as each
other.
[0121] X.sup.11 and X.sup.12 each independently preferably
represent --O--, --OC(.dbd.O)--, --OC(.dbd.O)O--, --OC(.dbd.O)NH--,
--C(.dbd.O)O--, --C(.dbd.O)NH--, --NHC(.dbd.O)--, or
NHC(.dbd.O)O--, more preferably represent --OC(.dbd.O)--,
--C(.dbd.O)O--, --OC(.dbd.O)NH--, or C(.dbd.O)NH--, and
particularly preferably represent --C(.dbd.O)O--.
[0122] L.sup.11 represents a divalent linking group or a single
bond linking X.sup.11 and P.sup.11 to each other. Examples of the
divalent linking group include --O--, --OC(.dbd.O)--,
--C(.dbd.O)O--, an alkylene group having 1 to 10 carbon atoms
(preferably 1 to 8 carbon atoms and more preferably 1 to 6 carbon
atoms), an arylene group having 6 to 20 carbon atoms (preferably 6
to 14 carbon atoms and more preferably 6 to 10 carbon atoms), a
group obtained by combining these, and the like. Examples of the
alkylene group having 1 to 10 carbon atoms include a methylene
group, an ethylene group, a propylene group, a butylene group, a
pentylene group, a hexylene group, and the like. Among these, a
methylene group, an ethylene group, a propylene group, and a
butylene group are preferable. Examples of the arylene group having
6 to 20 carbon atoms include a 1,4-phenylene group, a 1,3-phenylene
group, a 1,4-naphthylene group, a 1,5-naphthylene group, an
anthracenylene group, and the like. Among these, a 1,4-phenylene
group is preferable.
[0123] Each of the alkylene group and the arylene group may have a
substituent. The substituent includes substituents shown in a
substituent group Y, which will be described later, an alkyl group,
and an alkenyl group. The number of substituents is preferably 1 to
3, and more preferably 1. The substitution position is not
particularly limited. As the substituent, a halogen atom or an
alkyl group having 1 to 3 carbon atoms is preferable, and a methyl
group is more preferable. It is also preferable that the alkylene
group and the arylene group are unsubstituted. Particularly, it is
preferable that the alkylene group is unsubstituted.
[0124] P.sup.11 represents a functional group selected from the
group consisting of a (meth)acryl group, an oxiranyl group, an
oxetanyl group, a hydroxyl group, an amino group, a thiol group, an
isocyanate group, a carboxyl group, and a carboxylic acid anhydride
group. It is preferable that P.sup.11 represents an oxiranyl
group.
[0125] In a case where P.sup.11 represents a hydroxyl group,
L.sup.11 includes an arylene group, and it is preferable that
arylene group is bonded to P.sup.11.
[0126] Y.sup.12 represents a hydrogen atom, a linear, branched, or
cyclic alkyl group having 1 to 20 carbon atoms, or a group obtained
in a case where one methylene group or two or more methylene groups
in a linear, branched, or cyclic alkyl group having 1 to 20 carbon
atoms are substituted with --O--, --S--, --NH--, --N(CH.sub.3)--,
--C(.dbd.O)--, --OC(.dbd.O)--, or --C(.dbd.O)O--. In a case where
Y.sup.12 represents a linear, branched, or cyclic alkyl group
having 1 to 20 carbon atoms or a group obtained in a case where one
methylene group or two or more methylene groups in a linear,
branched, or cyclic alkyl group having 1 to 20 carbon atoms are
substituted with --O--, --S--, --NH--, --N(CH.sub.3)--,
--C(.dbd.O)--, --OC(.dbd.O)--, or --C(.dbd.O)O--. Y.sup.12 may be
substituted with a halogen atom. Examples of the linear or branched
alkyl group having 1 to 20 carbon atoms include a methyl group, an
ethyl group, a n-propyl group, an isopropyl group, a n-butyl group,
an isobutyl group, a sec-butyl group, a tert-butyl group, a
n-pentyl group, an isopentyl group, a neopentyl group, a
1,1-dimethylpropyl group, a n-hexyl group, an isohexyl group, a
linear or branched heptyl group, an octyl group, a nonyl group, a
decyl group, an undecyl group, and a dodecyl group. The number of
carbon atoms in the cyclic alkyl group is preferably 3 to 20, and
more preferably equal to or greater than 5. The number of carbon
atoms in the cyclic alkyl group is preferably equal to or smaller
than 10, more preferably equal to or smaller than 8, and even more
preferably equal to or smaller than 6. Examples of the cyclic alkyl
group include a cyclopropyl group, a cyclobutyl group, a
cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a
cyclooctyl group.
[0127] Y.sup.12 is preferably a hydrogen atom, a linear, branched,
or cyclic alkyl group having 1 to 20 carbon atoms, or an alkylene
oxide group having 1 to 20 carbon atoms, and more preferably a
linear or branched alkyl group having 1 to 12 carbon atoms or an
ethylene oxide group or propylene oxide group having 1 to 20 carbon
atoms.
[0128] Regarding specific examples of the compound represented by
General Formula (XI) shown above, those described in paragraphs
"0028" to "0036" in JP1995-281028A (JP-H07-281028A), JP1995-306317A
(JP-H07-306317A), paragraphs "0016" to "0018" in JP2005-156822A,
paragraphs "0067" to "0072" in JP2006-301614A, and Liquid Crystal
Handbook (published on 2000 from MARUZEN Co., Ltd.), pp. 330 to
333.
##STR00020##
[0129] In the formula, A.sup.2, A.sup.3, and A.sup.4 each
independently represent --CH.dbd. or --N.dbd., R.sup.17, R.sup.18,
and R.sup.19 each independently represent
*--X.sup.211--(Z.sup.21--X.sup.212).sub.n21-L.sup.21-P.sup.21 or
*--X.sup.211--(Z.sup.22--X.sup.222).sub.n22--Y.sup.22, * represents
a position bonded to a central ring, two or more among R.sup.17,
R.sup.18, and R.sup.19 represent
*--X.sup.211--(Z.sup.21--X.sup.212).sub.n21-L.sup.21-P.sup.21,
X.sup.211 and X.sup.212 each independently represent a single bond,
--O--, --C(.dbd.O)--, --OC(.dbd.O)--, --OC(.dbd.O)O--,
--OC(.dbd.O)NH--, --OC(.dbd.O)S--, --C(.dbd.O)O--, --C(.dbd.O)NH--,
--C(.dbd.O)S--, --NHC(.dbd.O)--, --NHC(.dbd.O)O--,
--NHC(.dbd.O)NH--, --NHC(.dbd.O)S--, --S--, --SC(.dbd.O)--,
--SC(.dbd.O)O--, --SC(.dbd.O)NH--, or SC(.dbd.O)S--, Z.sup.21 and
Z.sup.22 each independently represent an aromatic group as a
5-membered or 6-membered ring or a non-aromatic group as a
5-membered or 6-membered ring, L.sup.21 represents a divalent
linking group or a single bond linking X.sup.212 and P.sup.21 to
each other, P.sup.21 represents a substituent selected from the
group consisting of a (meth)acryl group, an oxiranyl group, an
oxetanyl group, a hydroxyl group, an amino group, a thiol group, an
isocyanate group, a carboxyl group, and a carboxylic acid anhydride
group, Y.sup.22 represents a hydrogen atom, a linear, branched, or
cyclic alkyl group having 1 to 20 carbon atoms, or a group obtained
in a case where one methylene group or two or more methylene groups
in a linear, branched, or cyclic alkyl group having 1 to 20 carbon
atoms are substituted with --O--, --S--, --NH--, --N(CH.sub.3)--,
--C(.dbd.O)--, --OC(.dbd.O), or --C(.dbd.O)O--, n.sup.21 and
n.sup.22 each independently represent an integer of 0 to 3, and in
a case where each of n.sup.21 and n.sup.22 is equal to or greater
than 2, a plurality of groups represented by Z.sup.21--X.sup.212
and Z.sup.22--X.sup.222 may be the same as or different from each
other.
[0130] It is preferable that all of R.sup.17, R.sup.18, and
R.sup.19 represent
*--X.sup.211--(Z.sup.21--Z.sup.212).sub.n21-L.sup.21-P.sup.21. It
is more preferable that all of R.sup.17, R.sup.18, and R.sup.19 are
the same as each other.
[0131] As X.sup.211, X.sup.212, X.sup.221, and X.sup.222, a single
bond and --OC(.dbd.O)-- are preferable.
[0132] Z.sup.21 and Z.sup.22 each independently represent an
aromatic group as a 5-membered or 6-membered ring or a non-aromatic
group as a 5-membered or 6-membered ring. Examples thereof include
a 1,4-phenylene group, a 1,3-phenylene group, a heterocyclic group,
and the like.
[0133] The aromatic group and the non-aromatic group described
above may have a substituent. The substituent includes substituents
shown in the substituent group Y, which will be described later, an
alkyl group, and an alkenyl group. The number of substituents is
preferably 1 or 2, and more preferably 1. The substitution position
is not particularly limited. As the substituent, a halogen atom or
a methyl group is preferable. As the halogen atom, a chlorine atom
or a fluorine atom is preferable. It is also preferable that the
aromatic group and the non-aromatic group are unsubstituted.
[0134] Examples of the heterocyclic ring include the following
heterocyclic rings.
##STR00021##
[0135] In the formulae, * represents a portion bonded to X.sup.211,
** represents a portion bonded to X.sup.212; A.sup.41 and A.sup.42
each independently represent methine or a nitrogen atom; and
X.sup.4 represents an oxygen atom, a sulfur atom, methylene, or
imino.
[0136] It is preferable that at least one of A.sup.41 and A.sup.42
represents a nitrogen atom. It is more preferable that both of
A.sup.41 and A.sup.42 represent a nitrogen atom. Furthermore, it is
preferable that X.sup.4 represents an oxygen atom.
[0137] L.sup.21 each independently represents a divalent linking
group or a single bond linking X.sup.212 and P.sup.21 to each
other, and has the same definition as L.sup.11 in General Formula
(XI). As L.sup.21, --O--, --C(.dbd.O)O--, an alkylene group having
1 to 10 carbon atoms (preferably 1 to 8 carbon atoms and more
preferably 1 to 6 carbon atoms), or a group obtained by combining
these is preferable.
[0138] P.sup.21 each independently represents a functional group,
and has the same definition as P.sup.11 in General Formula (XI).
The preferred range of P.sup.21 is the same as the preferred range
of P.sup.11 in General Formula (XI).
[0139] Y.sup.22 each independently represents a hydrogen atom, a
linear, branched, or cyclic alkyl group having 1 to 20 carbon
atoms, or a group obtained in a case where one methylene group or
two or more methylene groups in a linear, branched, or cyclic alkyl
group having 1 to 20 carbon atoms are substituted with --O--,
--S--, --NH--, --N(CH.sub.3)--, --C(.dbd.O)--, --OC(.dbd.O)--, or
--C(.dbd.O)O--. Y.sup.22 has the same definition as Y.sup.12 in
General Formula (XI), and the preferred range thereof is also the
same as the preferred range of Y.sup.12 in General Formula
(XI).
[0140] n.sup.21 and n.sup.22 each independently represent an
integer of 0 to 3. n.sup.21 and n.sup.22 each independently
preferably represent an integer of 1 to 3, and more preferably
represent 2 or 3.
[0141] Regarding the details and specific examples of the compound
represented by General Formula (XII), the description in paragraphs
"0013" to "0077" in JP2010-244038A can be referred to, and the
contents thereof are incorporated into the present
specification.
[0142] It is preferable that the compound represented by General
Formula (XI) or (XII) is a compound having a hydrogen bonding
functional group, because then the stacking is enhanced by reducing
the electron density, and hence a columnar aggregate is easily
formed. Examples of the hydrogen bonding functional group include
--OC(.dbd.O)NH--, --C(.dbd.O)NH--, --NHC(.dbd.O)--,
--NHC(.dbd.O)O--, --NHC(.dbd.O)NH--, --NHC(.dbd.O)S--,
SC(.dbd.O)NH--, and the like.
[0143] Specific examples of compounds particularly preferred as the
compound represented by General Formula (XI) and the compound
represented by General Formula (XII) include the following
compounds.
##STR00022## ##STR00023## ##STR00024## ##STR00025## ##STR00026##
##STR00027## ##STR00028## ##STR00029## ##STR00030## ##STR00031##
##STR00032## ##STR00033##
[0144] The compound represented by General Formula (XI) can be
synthesized based on the methods described in JP1995-306317A
(JP-H07-306317A), JP1995-281028A (JP-H07-281028A), JP2005-156822A,
and JP2006-301614A.
[0145] The compound represented by General Formula (XII) can be
synthesized based on the methods described in JP2010-244038A,
JP2006-76992A, and JP2007-2220A.
[0146] <Curing Agent>
[0147] The resin composition may contain a curing agent.
[0148] The curing agent is not particularly limited as long as it
is a compound having a functional group selected from the group
consisting of a hydroxyl group, an amino group, a thiol group, an
isocyanate group, a carboxyl group, and a carboxylic acid anhydride
group. It is preferable that the curing agent has a functional
group selected from the group consisting of a hydroxyl group, an
amino group, and a thiol group. The curing agent preferably has two
or more functional groups described above and more preferably has
two functional groups described above.
[0149] Examples of the curing agent include the curing agent for an
epoxy resin described in "0028" in JP4118691B, the amine-based
curing agent, the phenol-based curing agent, or the acid
anhydride-based curing agent described in "0016" to "0018" in
JP2008-13759A, the amine-based curing agent and the phenol-based
curing agent described in "0101" to "0150" in JP2013-227451A, and
the like.
[0150] Among these, the amine-based curing agent is particularly
preferable, and examples of compounds preferred as the amine-based
curing agent include 4,4'-diaminodiphenylmethane,
4,4'-diaminodiphenylether, 4,4'-diaminodiphenylsulfone,
4,4'-diamino-3,3'-dimethoxybiphenyl, 4,4'-diaminophenylbenzoate,
1,5-diaminonaphthalene, 1,3-diaminonaphthalene,
1,4-diaminonaphthalene, 1,8-diaminonaphthalene, and the like.
[0151] The content of the curing agent in the resin composition
with respect to the mass of total solid content in the resin
composition (the mass of the total solid content except for a
solvent) is preferably 90% by mass to 10% by mass, and more
preferably 80% by mass to 30% by mass.
[0152] [Curing Accelerator]
[0153] The resin composition may contain a curing accelerator.
Examples of the curing accelerator include triphenylphosphine,
2-ethyl-4-methylimidazole, a boron trifluoride amine complex,
1-benzyl-2-methylimidazole, and those described in paragraph "0052"
in JP2012-67225A.
[0154] The content of the curing accelerator in the resin
composition with respect to the mass of total solid content in the
resin composition (the mass of the total solid content except for a
solvent) is preferably 20% by mass to 0.1% by mass, and more
preferably 10% by mass to 1% by mass.
[0155] <Solvent>
[0156] The resin composition may be prepared as a solution.
[0157] The solvent of the aforementioned solution is not
particularly limited, but is preferably an organic solvent.
Examples of the organic solvent include ethyl acetate, methyl ethyl
ketone (MEK), dichloromethane, tetrahydrofuran (THF), and the
like.
[0158] <Use of Resin Composition>
[0159] In the resin composition of the present invention, the
surface of an inorganic substance is modified using a boronic acid
compound, and accordingly, the dispersibility of the inorganic
substance in an organic solvent, a water solvent, a resin, or the
like is improved. By exploiting such characteristics, the resin
composition can be applied to various fields as a pigment, a
catalyst, an electrode material, a semiconductor material, a heat
dissipation material, a thermally conductive material, a lubricant,
and the like. It is particularly preferable that the resin
composition of the present invention is used for forming a
thermally conductive material.
[0160] [Thermally Conductive Material]
[0161] The thermally conductive material is a material having
thermal conductivity. The thermally conductive material can be used
as a heat dissipation material such as a heat dissipation sheet,
and can be used for dissipating heat from various devices such as
power semiconductor devices.
[0162] The shape of the thermally conductive material is not
particularly limited, and can be molded to have various shapes
according to the use. Typically, the thermally conductive material
is preferably in the form of a film or sheet.
[0163] The thermally conductive material of the present invention
includes a cured substance of a resin composition containing a
surface-modified inorganic substance and an epoxy compound. The
cured substance can be prepared by a curing reaction of the resin
composition. The curing may be a thermal curing reaction or a
photocuring reaction, and the curing reaction may be selected
according to the functional group of the monomer in the resin
composition. Generally, a thermal curing reaction is preferable as
curing. The heating temperature at the time of the curing is not
particularly limited. For example, the heating temperature may be
appropriately selected within a range of 50.degree. C. to
200.degree. C. and preferably within a range of 60.degree. C. to
150.degree. C.
[0164] It is preferable that the curing is performed on the resin
composition formed into a film or sheet. Specifically, the resin
composition may be formed into a film by coating and subjected to a
curing reaction. At this time, press working may also be
performed.
[0165] The curing may be semi-curing. Furthermore, the thermally
conductive material may be disposed in a device to be used or the
like by being brought into contact with the device, and then
permanently cured by being further cured through heating or the
like. It is also preferable to allow the device and the thermally
conductive material of the present invention to stick to each other
through the heating or the like that is performed for the permanent
curing described above.
[0166] Regarding the preparation of the thermally conductive
material including the curing reaction, "Highly Thermally
Conductive Composite Material" (CMC Publishing CO., LTD., Yoshitaka
Takezawa) can be referred to.
Examples
[0167] Hereinafter, the present invention will be more specifically
described based on examples. The materials and reagents, the
amounts of substances and a ratio therebetween, the operation, and
the like described in the following examples can be appropriately
changed within a range that does not depart from the gist of the
present invention. Accordingly, the scope of the present invention
is not limited to the following examples.
[0168] <Formation of Self-Supported Film by Using Resin
Composition>
[0169] By mixing the materials in Table 1 together, a slurry was
prepared. A 2.0 cm.times.2.5 cm PET film (COSMOSHINE, manufactured
by Toyobo Co., Ltd., film thickness: 50 .mu.m) was coated with 1 mL
of the slurry by using a spin coater, thereby preparing a film
having a uniform surface shape. The film was disposed on a hot
plate, and the solvent was stepwise evaporated for 30 seconds at
60.degree. C., 30 seconds at 80.degree. C., and 30 seconds at
100.degree. C. Thereafter, the film was heated for 30 seconds at
160.degree. C., then cooled to room temperature, and peeled from
the PET film, thereby a self-supported film having a thickness of
about 400 .mu.m.
[0170] The materials in Table 1 were prepared as below.
[0171] [Main Agent]
[0172] (Disk-Like Liquid Crystal Compound 2)
[0173] According to the method described in examples in JP2696480B,
a compound TP-85 was synthesized and used as a disk-like liquid
crystal compound 2.
##STR00034##
[0174] (Disk-Like Liquid Crystal Compound 4)
[0175] According to the method described in examples in JP5385937B,
a trihydroxy substance shown below was synthesized. The substance
was alkylated based on the method described in examples in
JP2696480B and then oxidized using mCPBA, thereby obtaining a
disk-like liquid crystal compound 4 shown below.
##STR00035##
[0176] (Disk-Like Liquid Crystal Compound 6)
[0177] According to the method described in Example 13 in
JP5620129B, an intermediate shown below was synthesized. Then, the
intermediate was reacted with epichlorohydrin, thereby synthesizing
a disk-like liquid crystal compound 6.
##STR00036##
[0178] (Rod-Like Compound)
[0179] Rod-like compound 1: jER YL6121H (manufactured by Mitsubishi
Chemical Corporation)
[0180] Rod-like compound 2: jER 828US (manufactured by Mitsubishi
Chemical Corporation)
[0181] [Curing Agent]
[0182] Curing agent 1: 1,5-naphthalenediamine (manufactured by
TOKYO CHEMICAL INDUSTRY CO., LTD.)
[0183] Curing agent 2: 4,4'-diaminodiphenylmethane (manufactured by
TOKYO CHEMICAL INDUSTRY CO., LTD.)
[0184] Curing agent 3: 4,4'-diaminodiphenylsulfone (manufactured by
TOKYO CHEMICAL INDUSTRY CO., LTD.)
[0185] [Inorganic Substance]
[0186] Boron nitride 1 (hereinafter, described as BN1): BORONID
Cooling Filer AGGLOMERATE 50 (manufactured by 3M)
[0187] Boron nitride 2 (hereinafter, described as BN2): BORONID
Cooling Filer AGGLOMERATE 100 (manufactured by 3M)
[0188] Boron nitride 3 (hereinafter, described as BN3): DENKA BORON
NITRIDE FP70 (manufactured by Denka Company Limited.)
[0189] Alumina: AW70 (manufactured by Micron Co., Ltd.)
[0190] [Surface Modifier]
[0191] Boronic acid 1: p-hydroxyphenyl boronic acid (manufactured
by Wako Pure Chemical Industries, Ltd.)
[0192] Boronic acid 2: m-aminophenyl boronic acid (manufactured by
Wako Pure Chemical Industries, Ltd.)
[0193] [Measurement of Thermal Conductivity]
[0194] (1) By using "ai-Phase Mobile 1u" manufactured by ai-Phase
Co., Ltd., a coefficient of thermal diffusivity in a thickness
direction was measured.
[0195] (2) By using a balance "XS204" ("solid specific gravity
measuring kit" is used) manufactured by METTLER TOLEDO, the
specific gravity was measured.
[0196] (3) By using "DSC320/6200" manufactured by Seiko Instruments
Inc. and software of DSC7, the specific heat at 25.degree. C. was
determined under the heating condition of 10.degree. C./min.
[0197] (4) The obtained coefficient of thermal diffusivity was
multiplied by the specific gravity and the specific heat, thereby
calculating the thermal conductivity. The results are shown in
Table 1.
TABLE-US-00001 TABLE 1 Thermal Curing Inorganic Surface
conductivity Main agent g agent g substance g modifier g Solvent g
(W/m K) Example 1 Disk-like liquid 3 Curing 2.5 BN1 5 Boronic 0.05
MEK 5 13.4 crystal compound 2 agent 1 acid 1 Example 2 Disk-like
liquid 3 Curing 2.5 BN1 5 Boronic 0.05 MEK 5 13.2 crystal compound
2 agent 2 acid 1 Example 3 Disk-like liquid 3 Curing 2.5 BN1 5
Boronic 0.05 MEK 5 13.6 crystal compound 2 agent 3 acid 1 Example 4
Disk-like liquid 3 Curing 2.5 BN1 (80) + 5 Boronic 0.05 MEK 5 12.9
crystal compound 2 agent 1 alumina (20) acid 1 Example 5 Disk-like
liquid 3 Curing 2.5 BN2 5 Boronic 0.05 MEK 5 12.6 crystal compound
2 agent 1 acid 1 Example 6 Disk-like liquid 3 Curing 2.5 BN3 5
Boronic 0.05 MEK 5 13.1 crystal compound 2 agent 1 acid 1 Example 7
Disk-like liquid 3 Curing 2.5 BN1 5 Boronic 0.05 MEK 5 14.4 crystal
compound 2 agent 1 acid 2 Example 8 Disk-like liquid 3 Curing 2.5
BN1 5 Boronic 0.05 MEK 5 12.2 crystal compound 4 agent 1 acid 1
Example 9 Disk-like liquid 3 Curing 2.5 BN1 5 Boronic 0.05 MEK 5
12.1 crystal compound 4 agent 1 acid 2 Example 10 Disk-like liquid
3 Curing 2.5 BN1 5 Boronic 0.05 MEK 5 12.4 crystal compound 6 agent
1 acid 1 Example 11 Disk-like liquid 3 Curing 2.5 BN1 5 Boronic
0.05 MEK 5 13.2 crystal compound 6 agent 1 acid 2 Example 12
Rod-like compound 1 3 Curing 2.5 BN1 5 Boronic 0.05 MEK 5 9.5 agent
1 acid 1 Example 13 Rod-like compound 2 3 Curing 2.5 BN1 5 Boronic
0.05 MEK 5 9.1 agent 1 acid 1 Comparative Disk-like liquid 3 Curing
2.5 BN1 5 N/A 0.00 MEK 5 11.2 Example 1 crystal compound 2 agent 1
Comparative Disk-like liquid 3 Curing 2.5 BN1 5 N/A 0.00 MEK 5 10.9
Example 2 crystal compound 2 agent 2 Comparative Disk-like liquid 3
Curing 2.5 BN1 5 N/A 0.00 MEK 5 10.5 Example 3 crystal compound 2
agent 3 Comparative Disk-like liquid 3 Curing 2.5 BN1 (80) + 5 N/A
0.00 MEK 5 10.3 Example 4 crystal compound 2 agent 1 alumina (20)
Comparative Disk-like liquid 3 Curing 2.5 BN2 5 N/A 0.00 MEK 5 9.8
Example 5 crystal compound 2 agent 1 Comparative Disk-like liquid 3
Curing 2.5 BN3 5 N/A 0.00 MEK 5 9.6 Example 6 crystal compound 2
agent 1 Comparative Disk-like liquid 3 Curing 2.5 BN1 5 N/A 0.00
MEK 5 10.1 Example 7 crystal compound 4 agent 1 Comparative
Disk-like liquid 3 Curing 2.5 BN1 5 N/A 0.00 MEK 5 10.5 Example 8
crystal compound 6 agent 1 Comparative Rod-like compound 1 3 Curing
2.5 BN1 5 N/A 0.00 MEK 5 8.1 Example 9 agent 1 Comparative Rod-like
compound 2 3 Curing 2.5 BN1 5 N/A 0.00 MEK 5 7.3 Example 10 agent
1
[0198] From the results shown in the table, it is understood that
in all of the examples in which the boronic acid compound is used
as a surface modifier, the obtained thermal conductivity is higher
than that in the comparative examples in which the boronic acid
compound is not used.
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